A Calix[4]arene‐Based Cyclic Dinuclear Ruthenium Complex for Light‐Driven Catalytic Water Oxidation
Please always quote using this URN: urn:nbn:de:bvb:20-opus-230030
- A cyclic dinuclear ruthenium(bda) (bda: 2,2’‐bipyridine‐6,6’‐dicarboxylate) complex equipped with oligo(ethylene glycol)‐functionalized axial calix[4]arene ligands has been synthesized for homogenous catalytic water oxidation. This novel Ru(bda) macrocycle showed significantly increased catalytic activity in chemical and photocatalytic water oxidation compared to the archetype mononuclear reference [Ru(bda)(pic)\(_2\)]. Kinetic investigations, including kinetic isotope effect studies, disclosed a unimolecular water nucleophilic attack mechanismA cyclic dinuclear ruthenium(bda) (bda: 2,2’‐bipyridine‐6,6’‐dicarboxylate) complex equipped with oligo(ethylene glycol)‐functionalized axial calix[4]arene ligands has been synthesized for homogenous catalytic water oxidation. This novel Ru(bda) macrocycle showed significantly increased catalytic activity in chemical and photocatalytic water oxidation compared to the archetype mononuclear reference [Ru(bda)(pic)\(_2\)]. Kinetic investigations, including kinetic isotope effect studies, disclosed a unimolecular water nucleophilic attack mechanism of this novel dinuclear water oxidation catalyst (WOC) under the involvement of the second coordination sphere. Photocatalytic water oxidation with this cyclic dinuclear Ru complex using [Ru(bpy)\(_3\)]Cl\(_2\) as a standard photosensitizer revealed a turnover frequency of 15.5 s\(^{−1}\) and a turnover number of 460. This so far highest photocatalytic performance reported for a Ru(bda) complex underlines the potential of this water‐soluble WOC for artificial photosynthesis.…
| Author: | Frank WürthnerORCiDGND, Niklas Noll |
|---|---|
| URN: | urn:nbn:de:bvb:20-opus-230030 |
| Document Type: | Journal article |
| Faculties: | Fakultät für Chemie und Pharmazie / Institut für Organische Chemie |
| Language: | English |
| Parent Title (English): | Chemistry - A European Journal |
| Year of Completion: | 2021 |
| Volume: | 27 |
| Issue: | 1 |
| Pagenumber: | 444-450 |
| Source: | Chemistry - A European Journal (2021), 27 (1), 445-450. doi:10.1002/chem.202004486 |
| URL: | https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/chem.202004486 |
| DOI: | https://doi.org/10.1002/chem.202004486 |
| Dewey Decimal Classification: | 5 Naturwissenschaften und Mathematik / 54 Chemie / 547 Organische Chemie |
| Tag: | artificial photosynthesis; catalytic; dinuclear; homogenous catalysis; oxidation; photocatalysis; ruthenium; ruthenium complexes; water; water oxidation |
| Release Date: | 2021/03/09 |
| EU-Project number / Contract (GA) number: | 787937 |
| OpenAIRE: | OpenAIRE |
| Licence (German): |  CC BY-NC: Creative-Commons-Lizenz: Namensnennung, Nicht kommerziell 4.0 International |